經濟部中央標準局員工消费合作社印製 4 6 7 91 9 五、發明説明（1 ) 本發明係關於製備聚四氳呋喃、聚四氳呋喃共聚物或此 等聚合物之二酿或單酯之改良法，其是在至少—種短鏈調 聚劑及/或共聚單體之存在下，在經酸活化之鈣微晶高嶺石 上聚合四氫呋喃。 聚四氫呋喃（"PTHF")(亦即已知之聚（氧丁二醇））在塑膠 及合成纖維工業中係多用途之中間體，其特別是能用於製 備聚胺甲酸酯、聚酯及聚醯胺彈性體（其中其被當為二醇 成分）。此外，聚四氫呋喃及其某些衍生物於多種用法中係 有用之輔助劑’例如作為分散劑或用於脫墨廢紙。 工業上’ PTHF係經由適合之觸媒，於能控制聚合物鏈之 長度而因此能碉節平均分子量至所需值之試劑（鏈終止劑或 猶鏈調聚劑）之存在下，經四氫味喃之聚合作用而有效地製 備=經由選擇短鏈調聚劑之類型及數量即能提供該種控制 法。而選擇適合之短鏈調聚劑能於聚合物鏈之一‘或兩端 引進其他官能基。因此，例如，PTHF之單酯或二酯可使用 作為短鏈調聚劑之羧酸或羧酸酐而製備。 其他短鏈調聚劑不僅當為鏈終止劑，而且亦能插入增長 之PTHF聚合物鏈中。因此其可被視為共聚單體以及短鏈調 聚劑。此等共聚單體之實例係水及具有兩個羥基之短鏈調 聚劑（例如二酵）°此等二醇之實例為乙二醇、丁二醇、 1，4 -丁二醇' 1，6 -已二醇或低分子量pthf。適合之共聚單 體另有1，2 -伸燒基氧化物（例如環氧乙烷或環氧丙烷）、2 _ 甲基四氫呋喃或3 -甲基四氫味喃。除了水、^心丁二醇及 低分子量PTHF以外’使用此等共聚單體會形成四氫呋喃共 -4 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公楚） (請先閲讀背面之注意事項再填寫本頁) 一裝· 4 6 7 919 A7 B7 經濟部中央標準局負工消費合作社印製 五、發明説明（2) 聚物。以此種方式，可將PTHF化學改質。實例是使用短鏈 調聚劑2 - 丁炔-1，4 _二醇會導致pTHF聚合物鏈中存在部分 CUC叁鍵。由於此等叁鍵之反應性，因此以此種方式改質 之PTHF可於此等位置進行進一步之化學改質，例如經由叁 鍵之氳化作用成為雙鍵、經由之後與其他單體接枝以調整 聚合物之性質、經由交聯以生成比較剛性結構之聚合物、 或經由聚合物化學之其他習用之方法。亦可能完全氣化存 在之畚鏈且通常會導致具有特別低之色數（c〇l〇r nurnber)之 PTHF。 西德專利-B-1 226 560敘述製備聚四氫呋喃二乙酸酯之方 法。其係在漂白土觸媒之存在下，聚合四氫呋喃（THF)。 特別是使用微晶高嶺石類型的氫矽酸鋁或矽酸鋁/鎂（可經 酸活化者）。例如，商品名稱為”TonsiI®"之酸性微晶高嶺 石土與乙酐一起使用當為短鏈調聚劑。 西德專利1 226 560中敘述使用微晶高嶺石而獲得之 PTHF二乙酸酯具有相當高之阿法（APHA)色數。假若需要低 色數產物’則必須將根據西德專利-A~l 226 560所獲得之混 合物經另外之純化步驟。 世界智慧財產權組織專利（WO) 5>4/0；5719揭示經矽酸鋁 觸媒製備聚四亞甲基醚二醇二酯之方法。除了非晶形鋁矽 酸鹽或滞石以外，亦可以經酸活化及經烺燒之高嶺土取代 已知之天然微晶南嶺石。 根據西德專利-C-195 13 493，由作為觸媒之綠坡縷石類 型之氫矽酸鎂/鋁中製備聚四亞甲基醚二醇二酯。其宣稱， -5- 本紙法尺度適用中國國家標準（CNS > A4規格（210X297公嫠) --------Λ·..裝-- (請先閲讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 4 6 7 91 9 V. Description of the Invention (1) The present invention relates to the preparation of polytetramethylene furans, polytetramethylene furan copolymers or the second or monoesters of these polymers. An improved method is to polymerize tetrahydrofuran on acid-activated calcium microcrystalline kaolinite in the presence of at least one short-chain telomer and / or comonomer. Polytetrahydrofuran (" PTHF ") (also known as poly (oxybutanediol)) is a versatile intermediate in the plastics and synthetic fiber industry, which can be used in particular for the preparation of polyurethanes and polyesters. And polyamide elastomers (wherein they are considered to be diol components). In addition, polytetrahydrofuran and certain derivatives thereof are useful adjuncts' in a variety of applications, such as as a dispersant or for deinking waste paper. Industrially, PTHF is passed through a suitable catalyst in the presence of a reagent (chain terminator or chain telomer) capable of controlling the length of the polymer chain and thus capable of controlling the average molecular weight to a desired value. The effective preparation of Weinan = through selection of the type and amount of short chain telomers can provide this control method. The selection of a suitable short-chain telomer can introduce other functional groups at one or both ends of the polymer chain. Therefore, for example, a mono- or diester of PTHF can be prepared using a carboxylic acid or carboxylic anhydride as a short-chain telomer. Other short-chain telomers not only act as chain terminators, but can also be inserted into growing PTHF polymer chains. It can therefore be considered as a comonomer as well as a short chain telomer. Examples of these comonomers are water and short-chain telomers (eg, two enzymes) having two hydroxyl groups. Examples of these diols are ethylene glycol, butanediol, 1,4-butanediol '1 , 6-Hexanediol or low molecular weight pthf. Suitable comonomers are additionally 1,2-dextrin-based oxides (such as ethylene oxide or propylene oxide), 2-methyltetrahydrofuran or 3-methyltetrahydrofuran. Except for water, butanediol, and low molecular weight PTHF ', the use of these comonomers will form tetrahydrofuran co-4-This paper size applies to China National Standard (CNS) A4 (210X297). (Please read the back Please fill in this page again for precautions) One pack 4 6 7 919 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (2) Polymer. In this way, PTHF can be chemically modified. An example is the use of a short-chain telomer 2-butyne-1,4-diol which results in the presence of a partial CUC triple bond in the pTHF polymer chain. Due to the reactivity of these triple bonds, PTHF modified in this way can be further chemically modified at these positions, such as double bonds through the dehydration of triple bonds and subsequent grafting with other monomers. To adjust the properties of the polymer, cross-link to produce a polymer with a relatively rigid structure, or other conventional methods through polymer chemistry. It is also possible to completely vaporize the existing fluorene chains and usually result in PTHF with a particularly low color number (collor nurnber). West German Patent-B-1 226 560 describes a method for preparing polytetrahydrofuran diacetate. It polymerizes tetrahydrofuran (THF) in the presence of a bleaching earth catalyst. In particular, microcrystalline kaolinite-type aluminum hydrosilicate or aluminum silicate / magnesium (which can be activated by acid) is used. For example, acidic microcrystalline kaolinite with the trade name "TonsiI®" is used together with acetic anhydride as a short-chain telomerizer. West German Patent 1 226 560 describes the use of microcrystalline kaolinite to obtain PTHF diacetic acid. The ester has a relatively high APHA color number. If a low color number product is needed, then the mixture obtained according to the West German Patent A-l 226 560 must be subjected to an additional purification step. World Intellectual Property Rights Patent (WO ) 5> 4/0; 5719 discloses a method for preparing a polytetramethylene ether glycol diester via an aluminum silicate catalyst. In addition to an amorphous aluminosilicate or a pyrophyllite, it can also be activated by acid and sintered. Kaolin replaces the known natural microcrystalline nanolinite. According to West German Patent-C-195 13 493, polytetramethylene ether glycol is prepared from magnesium hydrosilicate / aluminum of the attapulgite type as a catalyst. Diester. It claims that -5- the paper size is applicable to Chinese national standards (CNS > A4 specification (210X297 cm)) -------- Λ · ..packing-- (Please read the precautions on the back first (Fill in this page again)
*1T 經濟部中央標準局貝工消費合作社印製 4 6 7 9 19 A7 B7 五、發明説明（3 ) 以此等觸媒取代已知之微晶高韻石、滞石或高嶺土觸媒會 導致較高之聚合速率且聚合物具有較一致之性質與有务子 量分布。 美國專利5,210,283敘述於酸酐之存在下，由一種經酸活 化之漂白土（其於使用前已於高於600°C之溫度烺燒）上製備 PTHF之方法。此種方法之優點係生成窄分子量分布之產 物，但色數未因而降低。 美國專利4,127,5 13敘述，在酸度為每克具0.1至〇,9毫當量 H+之經酸活化之微晶高嶺石上，將THF/伸烷基氧化物共聚 物中環狀寡聚物降至最低之方法；其中亦未提及色數之改 良。 美國專利4;228,272敘述對於美國專利4，127,513之改良 法，其係使用孔隙體積為0·4-0.8立方厘米/克、表面積為 220-260平方米/克及平均孔隙體積為0.1-0.3微米之經酸活 化之微晶高嶺石而達成。然而，所用之觸媒（來自蘇德奇米 公司（Siidchemie)之ΚΟ®)僅於聚合作用之最初階段中改良色 數。 無論如何，已知之觸媒系統不具足夠活性以於工業規模 進行該方法（特別是當使用工業級之THF時）。 由於不勻催化之PTHF法之經濟生存力係極賴於觸媒之生 產力及所獲產物之純度，因此，本發明之目的係提供用於 PTHF方法之觸媒，以能獲得較高之聚合物產量及較低之聚 合物色數。 吾等發現，於至少一種短鏈調聚劑及/或共聚單體之存 -6- 本紙張尺度逋用中國囡家橾率（CNS > ZU規格（210Χ297公釐） j I II I I HI .....— I—- t— (請先閲讀背面之注項再填寫本頁) 釘 " 4 67 9 1 b 經濟部中央標準局WC工消費合作社印裝 A7 B7 五、發明説明（4 ) 在下，在作為觸媒之經酸活化之鈣微晶高嶺石（該鈣微晶 南嶺石BET表面積是至少300平方米/克，於pKa<-3之酸度是 至少0_02毫莫耳/克及孔隙大小在3 〇至200埃（A)之範圍 時，孔隙體積至少是0.40立方厘米/克）上聚合四氫呋喃以 製備聚四氫吱喃、聚四氫呋喃共聚物或其二酯或單酯之 方法即可達成此種目的。 根據本發明使用之微晶高嶺石係黏土（特別是蒙脫石綠土 (smectite)類）。本發明法中，可使用天然或合成之微晶高嶺 石。較佳係使用天然之鈣微晶高嶺石。 微晶高嶺石觸媒被用於本發明法前，較佳先在酸中活 化。該活化法可根據例如’西德專利 -B-10 69 583或歐洲專利-A-0 398 636中敘述之方法進行。 多種酸可被用於酸活化法中，較佳者係習用之無機酸或有 機羧酸。此等酸較佳係選自包括氫氯酸、硫酸、硝酸、鱗 酸、甲酸、乙酸或檸檬酸。特別佳者係硫酸及/或氫氣酸。 酸活化作用係將粉末狀微晶高嶺石懸浮於酸中而達成， 懸浮液之固體含量（以懸浮液之總重量為基準）較佳為1至 70重量。/。’特別佳為20至60重量％ »酸濃度係视使用之酸 及黏土之類型而定。其可於極大範圍内改變，而較佳係於 2至100%範圍内。當使用硫酸及氫氯酸時，較佳濃度係2 〇 至5 0 %。懸浮液較佳係於3 〇至120。(：，特別佳為5 0至110 °C，較佳係歷時0.5至2 4小時’特別佳為1至1 5小時攪拌反 應。接著分離出經酸活化之微晶高嶺石（例如，經由過滤 法）’之後用蒸館水或去離子水洗滌以移除黏附之微量酸 -7- 本紙張尺度適用中國國家標芈（CNS ) A4規格（210X297公釐〉 (請先閲讀背面之注意事項再填寫本頁) 裝·* 1T Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4 6 7 9 19 A7 B7 V. Description of the invention (3) The replacement of known microcrystalline kaolinite, sludge or kaolin catalysts with these catalysts will result in higher The polymerization rate and the polymer have more consistent properties and distribution. U.S. Patent 5,210,283 describes a method for preparing PTHF from an acid-activated bleaching earth which has been calcined at a temperature above 600 ° C in the presence of acid anhydride. The advantage of this method is that a narrow molecular weight distribution product is produced, but the color number is not reduced as a result. U.S. Patent No. 4,127,513 describes the reduction of cyclic oligomers in THF / alkylene oxide copolymers on acid-activated microcrystalline kaolinite with an acidity of 0.1 to 0.9 milliequivalent H + per gram. The lowest method; the improvement of the color number is not mentioned. U.S. Patent No. 4; 228,272 describes an improvement to U.S. Patent No. 4,127,513, which uses a pore volume of 0.4-0.8 cm3 / g, a surface area of 220-260 m2 / g, and an average pore volume of 0.1-0.3 microns This is achieved by acid-activated microcrystalline kaolinite. However, the catalyst used (KO® from Siidchemie) only improved the color number during the initial stages of polymerization. In any case, the known catalyst systems are not sufficiently active to perform the process on an industrial scale (especially when using industrial grade THF). Since the economic viability of the unevenly catalyzed PTHF method is highly dependent on the productivity of the catalyst and the purity of the product obtained, the object of the present invention is to provide a catalyst for the PTHF method in order to obtain a higher polymer Yield and lower polymer color number. We have found that in the presence of at least one short-chain telomer and / or comonomer, we use the Chinese standard (CNS > ZU specification (210 × 297 mm) j I II II HI. ....— I—- t— (Please read the notes on the back before filling out this page) Pin " 4 67 9 1 b Printed by the WC Industrial Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (4 ) In the following, acid-activated calcium microcrystal kaolinite as a catalyst (the calcium microcrystal nanolinite has a BET surface area of at least 300 square meters / gram, and an acidity at pKa <-3 of at least 0_02 millimoles / gram And when the pore size is in the range of 30 to 200 angstroms (A) and the pore volume is at least 0.40 cubic centimeters / gram), a method for preparing polytetrahydrofuran, a polytetrahydrofuran copolymer or a diester or monoester thereof This purpose can be achieved. The microcrystalline kaolinite clay (especially smectite) used in the present invention. In the method of the present invention, natural or synthetic microcrystalline kaolinite can be used. It is natural calcium microcrystalline kaolinite. Microcrystalline kaolinite catalyst is preferably used before the method of the present invention. Activation in an acid. This activation method can be performed according to, for example, the method described in 'West German Patent-B-10 69 583 or European Patent-A-0 398 636. A variety of acids can be used in the acid activation method, preferably the It is a conventional inorganic acid or organic carboxylic acid. These acids are preferably selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, scale acid, formic acid, acetic acid or citric acid. Particularly preferred are sulfuric acid and / or hydrogen acid. Acid activation The action is achieved by suspending the powdery microcrystalline kaolinite in an acid, and the solid content of the suspension (based on the total weight of the suspension) is preferably 1 to 70% by weight. 'Particularly preferred is 20 to 60% by weight »Acid concentration depends on the type of acid and clay used. It can be changed within a wide range, but is preferably in the range of 2 to 100%. When sulfuric acid and hydrochloric acid are used, the preferred concentration is 2 〇 To 50%. The suspension is preferably 30 to 120. (:, particularly preferably 50 to 110 ° C, preferably 0.5 to 24 hours, particularly preferably 1 to 15 hours, the reaction is stirred. Acid-activated microcrystalline kaolinite is then isolated (eg, by filtration), and then steamed or deionized. Washed with water to remove traces of acid -7- adhesion of this paper scale applicable Chinese national standard Mi (CNS) A4 size (210X297 mm> (please read the Notes on the back to fill out this page) installed ·
，1T, 1T
(210><297公釐） 4S791 9 1 ^ A7 ^_________B7 五'發明説明（5) 再乾燥或烺燒。微晶高嶺石觸媒較佳係於周圍壓力及8 0至 200°C(較佳為1〇〇至15〇°C)乾燥1至20小時。觸媒亦可於減 壓及較低溫度下乾燥。乾燥之觸媒較佳於150至600°C(特別 佳為200至500°C，特別是300至500°C)烺燒0.5至12小時（較 佳為1至5小時）。酸活化作用亦可以任#其他習用方法完 成。例如，酸可經噴霧或捏合伴隨成型與微晶高嶺石接 觸。 觸媒較佳經由酸處理以洗除鹼金屬離子。為了確保高活 性’成品觸媒較佳包含（以總觸媒重量為基準）低於3重量 %，較佳低於2重量％之鹼金屬離子（於900 t烺燒後測 定）。 由於水是能與THF聚合短鏈調聚劑’因此當使用除了水 以外之短鏈調聚劑/共聚單體時，於使用之前較佳是將微晶 高嶺石觸媒於上述條件下乾燥及/或烺燒。 可用於本發明THF聚合法之根據本發明所能使用之觸媒 可為粉末形式（例如當於懸浮液中進行該方法時），或者較 佳為疋型體（例如圓柱型、球型、環型或顆粒塑），.特別當 觸媒係排列於固^纟時，Μ #使用例如環狀反應器或當該 方法係連續進行時，則此型式較佳。 用於製備PTHF二酯之適合短鏈調聚劑係衍生自 元羧酸之羧酸酐，例如乙酐、丙酐及丁酐。使用 鏈調聚劑所得之PTHF二㈣經由各.種方法轉化成 4如’美國專利4,46〇，？96中敘述者）。 用於製備PTHF單酿之短鍵調聚劑之—元幾酸通常係k -8 --------:裝-----..—4T------5.·^ (請先閲讀背面之注意事項再填寫本頁) A7 4 6 7 9 1 9 B7 五、發明説明（6 ) C20 - —元藏酸，特別佳為甲酸、乙酸、丙酸、2 -乙基己 酸、丙烯酸及甲基丙歸酸。 用於製備T H F共聚物之適合短鏈調聚劑之實例係1,4 - 丁 炔二醇。所得共聚物可接著經叁键之氫化作用而·轉化成 PTHF(但其本身亦顯示有趣之性質）。 其他THF共聚物可使用1,2.-伸烷基氧化物（較佳為環氧乙 板或ϊ哀氧丙燒）、2 -甲基四氨咬喃、3 -甲基四氮ρ夫喃、或 二醇（例如乙二醇或1，6 -己二醇）而獲得。 當使用短鏈.調聚劑水及/或1，4 - 丁二醇時，PTHF係以本 發明方法之單一步騾獲得。倘若需要，亦可能將具有200至 700道耳吞分子量之低分子量、開鏈之PTHF，以當為短鏈 調聚劑猶環至聚合反應中並轉化成較高分子量之PTHF。由 於1,4 -丁二醇及低分子量PTHF具有兩個羥基，因此其插入 PTHF鍵中不僅是末端作為短鍵調聚劑而且内部亦能作為單 體。 . 短鏈調聚劑適於以含於THF中之溶液加入聚合作用中。 由於短鏈調聚劑會終止聚合作用，因此PTHF或PTHF二酯 之平均分子量可經由所用短鏈調聚劑之量而加以控制。反 應混合物中存在之短鏈調聚劑量愈多，則PTHF或相關之 PTHF衍生物之平均分子量愈低。端賴於聚合混合物中之短 鏈調聚劑含量，而可以一種控制之方式製備具有250至 10,000道耳呑平均分子量之PTHF或相關之PTHF衍生物。本 發明方法較佳是用以製備平均分子量為500至10,000道耳呑 (特別佳是650至5,000道耳呑）之PTHF或相關之PTHF衍生 -9- 本紙張尺度適用中國國家標準（CMS ) A4規格（2l〇X29"7公釐） (請先閲讀背面之注意事項再填寫本頁) 裝-(210 > < 297 mm) 4S791 9 1 ^ A7 ^ _________ B7 Five 'invention description (5) Dry or burn. The microcrystalline kaolinite catalyst is preferably dried at ambient pressure and 80 to 200 ° C (preferably 100 to 150 ° C) for 1 to 20 hours. The catalyst can also be dried under reduced pressure and lower temperature. The dried catalyst is preferably calcined at 150 to 600 ° C (particularly 200 to 500 ° C, particularly 300 to 500 ° C) for 0.5 to 12 hours (preferably 1 to 5 hours). Acid activation can also be accomplished by any other conventional method. For example, the acid may be contacted with microcrystalline kaolinite by spraying or kneading accompanying molding. The catalyst is preferably treated with an acid to remove alkali metal ions. To ensure high activity, the finished catalyst preferably contains (based on the total catalyst weight) less than 3% by weight, preferably less than 2% by weight of alkali metal ions (measured after 900 t firing). Since water is capable of polymerizing short-chain telomers with THF, when using short-chain telomers / comonomers other than water, it is preferable to dry the microcrystalline kaolinite catalyst under the above conditions and / Or braised. The catalyst that can be used according to the present invention that can be used in the THF polymerization method of the present invention may be in the form of a powder (for example, when the method is performed in a suspension), or preferably a pseudo-type body (for example, a cylindrical type, a spherical type, a ring type (Type or granular plastic), especially when the catalyst system is arranged in a solid state, M # using, for example, a ring reactor or when the method is performed continuously, this type is better. Suitable short chain telomers for the preparation of PTHF diesters are carboxylic anhydrides derived from monocarboxylic acids, such as acetic anhydride, propionic anhydride and butyric anhydride. The PTHF difluorene obtained using a chain telomer is converted into 4 by various methods such as' U.S. Patent 4,46? Narrator 96). For short-term telomers used in the preparation of PTHF monomers, quinacid is usually k -8 --------: packing -----..— 4T ------ 5. · ^ (Please read the notes on the back before filling this page) A7 4 6 7 9 1 9 B7 V. Description of the invention (6) C20-Yuanzang acid, especially formic acid, acetic acid, propionic acid, 2-ethyl Caproic acid, acrylic acid and methacrylic acid. An example of a suitable short-chain telomer for the preparation of T H F copolymers is 1,4-butynediol. The resulting copolymer can then be converted into PTHF by hydrogenation of the triple bond (but it itself shows interesting properties). Other THF copolymers can use 1,2.-alkylene oxide (preferably ethylene oxide board or propylene oxide), 2-methyltetramine, and 3-methyltetrazine Or a diol (such as ethylene glycol or 1,6-hexanediol). When using short-chain.telomer water and / or 1,4-butanediol, PTHF is obtained in a single step of the process of the present invention. If necessary, it is also possible to convert low molecular weight, open-chain PTHF having a molecular weight of 200 to 700 channels, as a short-chain telogen to the polymerization reaction and convert it into higher molecular weight PTHF. Since 1,4-butanediol and low-molecular-weight PTHF have two hydroxyl groups, their insertion into the PTHF bond is not only a terminal as a short-bond telomer but also an internal monomer. Short chain telomers are suitable for addition to polymerization as a solution in THF. Since the short chain telomer will terminate the polymerization, the average molecular weight of the PTHF or PTHF diester can be controlled by the amount of the short chain telomer. The more short-chain telomers present in the reaction mixture, the lower the average molecular weight of PTHF or related PTHF derivatives. Depending on the content of the short-chain telomer in the polymerization mixture, PTHF or related PTHF derivatives having an average molecular weight of 250 to 10,000 channels can be prepared in a controlled manner. The method of the present invention is preferably used to prepare PTHF or related PTHF derivatives with an average molecular weight of 500 to 10,000 channels (especially 650 to 5,000 channels) -9- This paper applies Chinese National Standard (CMS) A4 Specifications (2l0X29 " 7mm) (Please read the precautions on the back before filling this page)
Η-, P 經濟郎中夬樣_局貝工消费合作枉印软 4 6 7 9 | 9 Α7 Β7 經濟部中央標準局貝工消費合阼狂印裝 五、發明説明（7 ) 物。 聚合作用通常係於〇至80°C，較佳係於25°C至T H F之滞騰 溫度進行。由於使用之壓力對於聚合作用之結果通常不是 重要的’因此除了 THF與揮發性1,2-伸烷基氧化物之共聚 作用（其係適於在超大氣壓力下進行）以外，聚合作用通常 係於大氣壓力或聚合作用系統之本身產生之壓力下進行。 壓力通常為0,1至20巴，較佳為0,5至2巴之範園内。 為了避免醚過氧化物之生成，聚合作用適於在惰性氣體 大氣下進行。可使用之惰性氣體係，例如，氮、二氧化碳 或惰性氣體，而較佳為氮氣。 於氫大氣下進行聚合作用特別佳。此種具體實施例產生 色數特別低之聚合物。於此種情沉中，氫分壓可為0.1至5〇 巴。當於氫之存在下進行聚合作用時，經由鈣微晶高嶺石 摻雜元素週期表之族VII至X過渡金屬（例如釕、鍊、鎳、 鐵、姑、飽及/或銷）可進一步改良色數。 本發明方法可分批或連續進行，由於經濟理.由，較佳是 連續方法。 於分批法中，通常將THF、相關之短鏈調聚劑及觸媒於 上述之溫度，於攪拌槽或環形反應器中反應，直到達成需 要之THF轉化率為止。反應時間視加入之觸媒量可為0.5至 4 0小時，較佳為1 - 3 0小時。通常用於聚合作用中觸媒之量 係根據所用THF之重量為基準，而為1-90重量％，較佳為 4 - 7 0重量％，特別佳為8 - 6 0重量％。 於分批法中，經由移除流出物中存在之觸媒處理反應流 -10- 本紙張尺度通用中國國家搮隼（CNS ) A4规格（210X297公釐） ---------裝----^---1Τ-----:、線 f請先閲讀背面之注意事項再填寫本頁j 4 6 7 9 19 A7 __ B7 五、發明説明（8) 出物，一般處理法為料、傾析或離心。*含觸媒之聚合 作用流出物通常經由蒸餾處理，此情況中，較佳是將末轉 化之THF蒸餾出’且若需要，於減壓下經由蒸餘而自聚合 物中移除低分子量PTHF寡聚物。 根據本發明方法所製得特別具活性之觸媒是將鈣微晶高 嶺石經酸活化作用，此種方法致使其BET表面積是至少3〇〇 平方米/克，於PKa<·3之酸度是至少〇〇2毫莫耳/克及孔隙大 小在3〇至200埃（A)之範圍時，孔隙體積至少是〇4〇立方厘 米/克β BET表面積（5-點方法）及孔隙體積係得自氮吸附/去吸附 等溫線。30至200埃範圍内之孔隙體積係經由分析BJH去 吸附分布而測定。最後’平均孔隙直徑為2 〇 〇埃之累積孔 隙體積減去在3 0埃之累積孔隙體積。酸度係對哈梅特 (Hammett)指示劑二亞桂皮基丙酮之滴定（pKa=_3〇)而測 定’如塔那布（Tanabe)等人所發表之「新穎之固體酸與·驗 (New Solid Acids and Bases)」’表面科學觸媒之研究（stud. Surf· Sci· Catal.) 51，1989 ’ 第二章，及貝尼西（Benesi)發表 於物理化學雜誌（J..Phys,Chem.) 61，1957，970-973中之詳 述。為了測定酸度，將乾燥之觸媒懸浮於惰性非質子性溶 劑（如甲苯）中，接著將pKa限定為_3之指示劑及正丁基胺或 相似之驗加入。由於固體酸與驗之反應緩慢，因此不能以 習用法由滴定管進行滴定，而是將增量之驗加入多個批量 中’搖動混合物過夜，並於第二天早晨，於平衡之後，檢 查測定何量之鹼造成顏色改變。因此獲得定量測量之酸度 -11 - 木紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐} 威-- (請先閱讀背面之注意事項再填寫本頁) 訂 467919 A7 · B7 五、發明説明（θ ) 1 中〜值，其是於每克低於指示劑之pKa(即_ 3 )之固體酸所需 亳莫耳驗。 鈣微晶高嶺石較佳具有300至400平方米/克之BET表面 積。於pKa<-3之酸度較佳為0.02至〇1毫莫耳/克。孔隙大小 在30至200埃之範圍内時，孔隙體積較佳為〇4至1〇立方厘 米/克。 目前已知用於THF聚合作用之觸媒（T〇nsil®、K1〇®、 ΚΟ®、KSF®、ΚΡΙΟ®及其他（見西德專利π」226 560、西德 專利-Α-28 01 *792、美國專利4,228,272))係經由酸活化作用 而自鈉微晶高嶺石製備，其不符合本發明關於bet表面 積、孔隙體積及酸度之要求。 下列實例舉例說明本發明。 實例 觸媒製備 比較觸嫫V1 . v · 比較觸媒V 1係經酸活化之鈉微晶高嶺石（來自蘇德奇米 公司之Tonsil Optimum 210 FF®)，其B ET表面積為239平方 米/克、於3 0至200埃之範園内之孔隙體積為o.w立方厘米/ 克之及於pKa<-3之酸度為零" 比較觸媼V 2 比較觸媒V2係經酸活化之鈣微晶高嶺石（來自蘇德奇米 公司之K10®)，其BET表面積為270平方米/克、於30至200 埃之範圍内之孔隙體積為0.35立方厘米/克及於pKa<-3之酸 度為0.037毫莫耳/克。 12- 本紙張尺度適;！]中國國家標準（CNS ) A4規格（210X297公釐) {請先閱讀背面之注意事項再填寫本頁) 裝. -訂 經濟部中央榡準局貝工消費合作枉印裝 46 19 經濟却中央捸準馬員工消費合泎杜印製 A7 B7 五、發明説明（10) 觸媒Α係經酸活化之鈣微晶高嶺石（來自拉波提公司 (Laporte)之XMP-4®) ’其BET表面積為3 27平方米/克、於 3 〇至200埃之範園内之孔隙體積為0.56立方厘米/克及於 pKa<-3之酸度為0.042毫莫耳/克。 較觸嫫V3 比較觸媒V3係由比較觸媒V2之擠製物詛成。為了此種 目的，於捏合機中將K 1 0粉末與水混合並於擠製機中捣 製。然後將生成之擠製物於350°c烺燒= 也較觸嫫V 4 比較觸媒V4係BET表面積為264平方米/克之經酸活化之 鈉微晶高嶺石（來自蘇德奇米公司之KO®)。 觸媒B係由觸媒A之擠製物組成。為了此種目的，於捏合 機中將XMP-4粉末與水混合並於擠製機中擠製。然後將生 成之擠製物於350°C烺燒。 聚合作用 t例1 將182克四1呋喃及1 8克乙酐加入500毫升攪拌燒瓶中並 將之加熱至50°C。將10克觸媒於攪拌下（每分鐘180轉）加入 並於50°C攪拌混合物45分鐘。接著使用壓濾機將觸媒過濾 出並測定濾液之色數。然後於旋轉蒸發器上蒸發濾液（150 °C/1013毫巴30分鐘及150°C/〇.2-0.3毫巴30分鐘）。稱重所 得PTHF二酯以測定轉化率。 -13 - 本紙張尺度適用中國國家標準（CNS > A4规格（2丨0><297公釐） (請先聞讀背面之注意事項再填、寫本耳i 裝 五 4 6 7 9 19 A7 __ B7 發明説明（11) 結果示於表1。 表1 觸媒 轉化率[%] 濾液之色數 ΓΑΡΗΑ1 VI 8.3 25 V2 28.9 15 A 34.4 5 —. V4 15.3 17 實例清楚地顯示本發明之觸媒優於先前技藝之比較觸媒 V1、V2及V4:轉化率較高但色數較低。 —-------裝— (請先閱讀背面之注項再填寫本頁) 訂 一擇 實例2 將1·2升每一類之觸媒擠製物充填於循環反應器中。將 T H F/乙酐混合物（6·9重量。/0乙酐）以60毫升/小時作為進料 填充反應器（向下流動方式，溢流系統）；循環速率是8升/ 小時。以相同之循環速率，於13天後將進料增加至90毫升 /小時並於3 3天後增加至120毫升/小時。每天測定流出物之 色數然後於旋轉蒸發器上蒸發流出物（150°C/1013毫巴30分 鐘及150°C/0.2-0.3毫巴30分鐘）。稱重所得PTHF二酯以測 -14 - 本紙張尺度通用中國國家標準（CNS ) A4规格（210X297公釐） 丨·.··^ 經濟部中央標準局貝工消費合作社印裝 ^679 --—,五 .—___________B7、發明説明（12 ) 疋轉化率。將觸媒V3^B之結果，於其個別設定值示於表 2中。於每種之40天之運轉時間内未觀察到去活化作用： 每一時間轉化率及流出物之色數皆固定。於每種情況中分 子量係約900道耳呑。 表2 觸媒 ί~~~~Τϋ~~Γ 進料[毫升/小時] 轉化率[%] 滤液之色數 — -----— ΓΑΡΗΑ1 .V3 60 57.5 100 B 60 57.5 90 V3 90 55.5 150 B 90 55.5 90 V3 120 54.0 150 B 120 --------- 54.0 90 比較結果顯示’根據本發明之觸媒B於相同之（平衡）轉化 率下產生較比較觸媒V3顯著低之色數，於最初階段中，觸 媒B亦顯著較快達到平衡狀態，此反映其較高之活性。 (請先閱讀背面之注意事項再填寫本頁) 裝.Η-, P Economic Langzhong _ _Bei Pakong consumer cooperation seal soft 4 6 7 9 | 9 Α7 Β7 Central Standards Bureau of the Ministry of Economic Affairs Pui Bong consumer seals printed in five. Description of invention (7). The polymerization is usually carried out at a temperature of 0 to 80 ° C, preferably at a stagnation temperature of 25 ° C to THF. Since the pressure used is usually not important for the result of the polymerization, so in addition to the copolymerization of THF with a volatile 1,2-alkylene oxide (which is suitable for superatmospheric pressure), the polymerization is usually Under atmospheric pressure or pressure generated by the polymerization system itself. The pressure is usually in the range of 0,1 to 20 bar, preferably 0,5 to 2 bar. In order to avoid the formation of ether peroxide, the polymerization is suitable to be carried out under an inert gas atmosphere. An inert gas system that can be used is, for example, nitrogen, carbon dioxide or an inert gas, and nitrogen is preferred. Polymerization is particularly preferred under hydrogen atmosphere. This embodiment produces a polymer with a particularly low color number. In this case, the hydrogen partial pressure can be 0.1 to 50 bar. When the polymerization is performed in the presence of hydrogen, the transition metals (eg, ruthenium, chain, nickel, iron, iron, saturated, and / or pins) of the Group VII to X of the periodic table of calcium microcrystalline kaolinite doped elements can be further improved Color number. The method of the present invention can be carried out batchwise or continuously. For economic reasons, a continuous method is preferred. In a batch process, THF, related short-chain telomers and catalysts are usually reacted in a stirred tank or a ring reactor at the above temperatures until the required THF conversion is achieved. The reaction time may be 0.5 to 40 hours, preferably 1 to 30 hours, depending on the amount of catalyst added. The amount of the catalyst usually used in the polymerization is 1 to 90% by weight, preferably 4 to 70% by weight, and particularly preferably 8 to 60% by weight, based on the weight of the THF used. In the batch method, the reaction stream is processed by removing the catalyst present in the effluent. -10- This paper size is in accordance with China National Cricket (CNS) A4 specification (210X297 mm). ---- ^ --- 1Τ ----- :, line f, please read the precautions on the back before filling in this page j 4 6 7 9 19 A7 __ B7 V. Description of the invention (8) Product, general treatment The method is feed, decantation or centrifugation. * The catalyst-containing polymerization effluent is usually treated by distillation. In this case, it is preferred to distill off the unconverted THF 'and, if necessary, to remove low molecular weight PTHF from the polymer via distillation under reduced pressure. Oligomer. A particularly active catalyst prepared according to the method of the present invention is the activation of calcium microcrystalline kaolinite by acid. This method results in a BET surface area of at least 300 square meters per gram. The acidity at PKa <· 3 is At least 0.02 millimoles / g and pore size in the range of 30 to 200 Angstroms (A), the pore volume is at least 0.40 cm3 / g β BET surface area (5-point method) and pore volume Self-nitrogen adsorption / desorption isotherms. The pore volume in the range of 30 to 200 Angstroms is determined by analyzing the BJH desorption profile. Finally, the average pore diameter is the cumulative pore volume of 200 Angstroms minus the cumulative pore volume at 30 Angstroms. The acidity is determined by the titration (pKa = _3〇) of Hamnett's indicator diarthinylacetone (such as "New Solid Acid and Test (New Solid) published by Tanabe et al." Acids and Bases) "'Studies in Surface Science Catalysts (stud. Surf · Sci · Catal.) 51, 1989' Chapter 2, and Benesi published in the Journal of Physical Chemistry (J .. Phys, Chem. ) 61, 1957, 970-973. In order to determine the acidity, the dry catalyst is suspended in an inert aprotic solvent (such as toluene), and the indicator with pKa limited to _3 and n-butylamine or similar are added. Because the solid acid reacts slowly with the test, it cannot be titrated by a burette in the usual way. Instead, add incremental tests to multiple batches. Shake the mixture overnight, and the next morning, after equilibration, check to determine what The amount of alkali causes a change in color. So get the quantitative measurement of acidity -11-The size of wood paper is applicable to Chinese National Standard (CNS) A4 specification (210X297mm) Wei-(Please read the precautions on the back before filling this page) Order 467919 A7 · B7 V. Invention Explanation (θ) 1 is a value of ~, which is a mole test per gram of solid acid lower than the pKa of the indicator (ie, _3). The calcium microcrystalline kaolinite preferably has 300 to 400 square meters per gram. The BET surface area. The acidity at pKa < -3 is preferably 0.02 to 0.01 millimoles / g. When the pore size is in the range of 30 to 200 angstroms, the pore volume is preferably 0.4 to 10 cm3 / g. Catalysts currently known for the polymerization of THF (Tonsil®, K1〇®, KO®, KSF®, KPIO® and others (see West German patent π "226 560, West German patent -A-28 01 * 792, US Patent 4,228,272)) is prepared from sodium microcrystalline kaolinite through acid activation, which does not meet the requirements of the present invention regarding bet surface area, pore volume, and acidity. The following examples illustrate the invention. Example Catalyst Preparation嫫 V1. V · Comparative catalyst V 1 is acid-activated sodium microcrystalline kaolinite (lai Sudzimi's Tonsil Optimum 210 FF®) has a B ET surface area of 239 square meters per gram, a pore volume in the range of 30 to 200 angstroms, ow cubic centimeters per gram, and zero acidity at pKa < -3 " Comparative catalyst V 2 Comparative catalyst V 2 is acid-activated calcium microcrystalline kaolinite (K10® from Sudzimi Corporation), with a BET surface area of 270 square meters per gram, in the range of 30 to 200 Angstroms. The pore volume is 0.35 cubic centimeters / gram and the acidity at pKa < -3 is 0.037 millimoles / gram. 12- The size of this paper is suitable ;!] Chinese National Standard (CNS) A4 specification (210X297 mm) {Please read first Note on the back, please fill in this page again.) Packing.-Order the printing and packaging of the shellfish consumer cooperation of the Central Economic and Technical Bureau of the Ministry of Economic Affairs. Catalyst A is an acid-activated calcium microcrystalline kaolinite (XMP-4® from Laporte). Its BET surface area is 3 27 square meters per gram in the range of 30 to 200 angstroms. The pore volume was 0.56 cubic centimeters / gram and the acidity at pKa < -3 was 0.042 millimoles / gram. Comparative catalyst V3 Comparative catalyst V3 is cursed from the extrusion of comparative catalyst V2. For this purpose, the K 10 powder is mixed with water in a kneader and compacted in an extruder. The resulting extrudate was then fired at 350 ° C = also more reactive than V 4 compared to catalyst V 4 based on acid-activated sodium microcrystalline kaolinite with a BET surface area of 264 m 2 / g (KO® from Sudzimi Corporation). ). Catalyst B is composed of the extruded product of Catalyst A. For this purpose, the XMP-4 powder is mixed with water in a kneader and extruded in an extruder. The resulting extrudate was then fired at 350 ° C. Polymerization Example t1 182 g of tetrafuran and 18 g of acetic anhydride were put in a 500 ml stirred flask and heated to 50 ° C. 10 grams of catalyst was added with stirring (180 rpm) and the mixture was stirred at 50 ° C for 45 minutes. The catalyst was then filtered out using a filter press and the color number of the filtrate was measured. The filtrate was then evaporated on a rotary evaporator (150 ° C / 1013 mbar for 30 minutes and 150 ° C / 0.2-0.3 mbar for 30 minutes). The obtained PTHF diester was weighed to determine the conversion. -13-This paper size applies to Chinese national standards (CNS > A4 specifications (2 丨 0 > < 297 mm) (Please read the precautions on the back before filling and writing the ears.) 5 4 6 7 9 19 A7 __ B7 Description of the invention (11) The results are shown in Table 1. Table 1 Catalyst conversion rate [%] Color number of filtrate ΓΑΡΗΑ1 VI 8.3 25 V2 28.9 15 A 34.4 5 —. V4 15.3 17 The example clearly shows the catalyst of the present invention Comparison catalysts V1, V2, and V4 that are superior to previous techniques: higher conversion rate but lower color number. —------- install— (Please read the note on the back before filling this page) Order one Example 2 A 1,2 liter catalyst extrudate of each type was charged into a circulation reactor. A THF / acetic anhydride mixture (6.9 wt./0 acetic anhydride) was used to fill the reactor with 60 ml / hour as a feed. (Downflow method, overflow system); circulation rate is 8 liters / hour. At the same circulation rate, increase the feed to 90 ml / hour after 13 days and increase to 120 ml / hour after 33 days Measure the color number of the effluent every day and then evaporate the effluent on a rotary evaporator (150 ° C / 1013 mbar for 30 minutes and 150 ° C / 0.2-0.3 mbar 3 0 minutes). Weigh the obtained PTHF diester to measure -14-This paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) 丨 ·. · ^ ^ Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ 679 ---, five. — ___________ B7. Description of the invention (12) 疋 Conversion rate. The results of the catalyst V3 ^ B are shown in Table 2 at their individual setting values. Within 40 days of each operation time Deactivation was observed: The conversion rate and the color number of the effluent were fixed at each time. In each case, the molecular weight was about 900 ears. Table 2 Catalyst ί ~~~~ Τϋ ~~ Γ Feed [ml / Hour] Conversion rate [%] Number of colors of filtrate — -----— ΓΑΡΗΑ1 .V3 60 57.5 100 B 60 57.5 90 V3 90 55.5 150 B 90 55.5 90 V3 120 54.0 150 B 120 ------- -54.0 90 The comparison shows that 'catalyst B according to the present invention produces significantly lower color numbers than the comparable catalyst V3 at the same (balanced) conversion rate. In the initial stage, catalyst B also reached equilibrium significantly faster. Status, which reflects its higher activity. (Please read the precautions on the back before filling this page).
JT 經濟部中央標準局員工消費合作社印製 -15- 本紙張尺度ϋ财關家縣（⑽）A4規格（2mx297公瘦）Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs of the JT -15- This paper is standard A4 size (2mx297)